Analysis System

Abstract

In one aspect, an analytical system is provided that uses a new indicator for the preparation of recycled processing liquid. [Solution] In one aspect, the present disclosure relates to an analysis system including: a carbonate concentration determination unit that determines the concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained by treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in liquid C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in liquid A, which contains an aliphatic quaternary ammonium hydroxide in the same amount as the aliphatic quaternary ammonium hydroxide consumed in neutralizing the carbon dioxide in liquid C.

Description

[Technical Field]

[0001] The present disclosure relates to an analysis system, a substrate processing system, a resin mask stripping method, and a method for manufacturing an electronic component. [Background technology]

[0002] In recent years, personal computers and various electronic devices have become increasingly power-efficient, faster, and more compact, and the wiring on the package substrates and other components they are equipped with has been getting finer every year. Until now, metal masking has been the primary method used to form such fine wiring and connection terminals such as pillars and bumps, but due to its limited versatility and the difficulty of adapting to the miniaturization of wiring, new methods are being adopted.

[0003] One new method is to use a dry film resist as a thick resin mask instead of a metal mask. This resin mask is finally peeled off and removed, and alkaline processing liquids (stripper compositions, stripping cleaners) are used for this purpose.

[0004] As an alkaline processing liquid (stripper composition), a mixed solution of an alkali, an organic solvent, etc. is used. It has been reported that such processing liquid (stripper composition) deteriorates due to dissolution of the resist, reaction with carbon dioxide gas in the air, etc., and stripping performance (resin mask removability) decreases. Therefore, various methods for suppressing the deterioration of the processing liquid (stripper composition) and extending its life have been investigated. For example, Patent Document 1 has discovered that carbon dioxide gas absorbed into a resist stripping solution is the main cause of reduced resist stripping properties, and has proposed a method for managing the resist stripping solution to maintain the carbon dioxide gas concentration in the resist stripping solution at 3% by weight or less. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-122029 Summary of the Invention [Problem to be solved by the invention]

[0006] When forming fine wiring on a printed circuit board or the like, a treatment liquid (stripper composition) is required to have high stripping performance (resin mask removability and cleaning ability) in order to reduce not only the residue of the resin mask but also the residue of auxiliary agents contained in the solder or plating solution used in the formation of the fine wiring or bumps. Furthermore, when the treatment liquid (stripper composition) is recycled, the alkaline components in the treatment liquid (stripper composition) and the carbon dioxide concentration present in the treatment liquid (stripper composition) change, so the treatment liquid (stripper composition) needs to be replenished or replaced depending on the concentration analysis results. The amounts and mixing ratios of the replenished components need to be controlled so that the composition of the treatment liquid (stripper composition) is appropriately maintained and the resin mask removability (strippability) does not decrease. For example, when an aliphatic quaternary ammonium hydroxide such as TMAH is used as one of the components of a treatment liquid (stripper composition), the aliphatic quaternary ammonium hydroxide is consumed to neutralize carbonate ions dissolved in the treatment liquid (stripper composition). In some cases, the aliphatic quaternary ammonium hydroxide feedstock solution contains some of the other stripping agent components, such as alkanolamine. When preparing a recycled treatment liquid by adding the above-mentioned feedstock liquid to a used treatment liquid containing carbon dioxide, a new indicator for use in the preparation is considered to be necessary in order to prevent a decrease in the functionality of the recycled treatment liquid.

[0007] Therefore, the present disclosure provides an analysis system using a new index for preparing a reused treatment liquid, a substrate processing system having the analysis system, a method for stripping a resin mask, and a method for manufacturing electronic components. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to an analysis system including: a carbonate concentration determination unit that determines the concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained after treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in liquid C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in liquid A, which contains an aliphatic quaternary ammonium hydroxide in an amount equivalent to the amount of aliphatic quaternary ammonium hydroxide consumed for neutralization of the carbon dioxide in liquid C.

[0009] In one aspect, the present disclosure relates to an analysis system including: a carbonate concentration determination unit that determines the concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained after treating a substrate having a resin mask with a treatment liquid obtained by using a mixture of an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine and an aqueous solution (liquid B) containing an organic solvent and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in liquid C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in liquid A, which contains an aliphatic quaternary ammonium hydroxide in an amount equivalent to the amount of aliphatic quaternary ammonium hydroxide consumed for neutralization of the carbon dioxide in liquid C.

[0010] In one aspect, the present disclosure relates to a substrate processing system including a substrate processing apparatus that processes a substrate having a resin mask using a processing liquid obtained by using an aqueous solution (Liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; an analysis system of the present disclosure; and a reuse processing liquid production unit that replenishes the processing liquid (Liquid C) after processing the substrate having the resin mask with a replenisher based on the amount of alkanolamine determined by the analysis system, thereby producing a reuse processing liquid for use in the substrate processing apparatus.

[0011] In one aspect, the present disclosure relates to a method for stripping a resin mask, including stripping the resin mask from a substrate having the resin mask thereon using the substrate processing system of the present disclosure.

[0012] The present disclosure relates to a method for manufacturing an electronic component substrate, including the resin mask peeling method of the present disclosure. [Effects of the Invention]

[0013] According to one or more embodiments of the present disclosure, an analysis system using a new index for preparing a reused treatment liquid can be provided. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram showing an embodiment of a substrate processing system according to the present disclosure. [Figure 2] FIG. 2 is a flow chart illustrating an embodiment of the operation of the analysis system in the substrate processing system of the present disclosure. [Figure 3] FIG. 3 is a schematic diagram showing an example of the appearance of the substrate surface of the substrate to be processed. DETAILED DESCRIPTION OF THE INVENTION

[0015] [Analysis System] When the processing liquid (stripping agent composition) is recycled, as described above, the alkaline component in the processing liquid (stripping agent composition) and the concentration of carbon dioxide present in the processing liquid (stripping agent composition) change, and therefore it is necessary to replenish or replace the processing liquid (stripping agent composition) depending on the concentration analysis results. Carbonic acid in the treatment liquid (stripper composition) can be neutralized using a strong alkali, aliphatic quaternary ammonium hydroxide. Therefore, when replenishing a treatment liquid (stripper composition) containing carbonic acid with an aqueous solution of aliphatic quaternary ammonium hydroxide, the replenishing amount of the aqueous solution of aliphatic quaternary ammonium hydroxide includes not only the amount necessary for the resin mask stripping treatment but also the amount necessary for neutralizing the carbonic acid. The aqueous solution of aliphatic quaternary ammonium hydroxide to be replenished may contain alkanolamines. As a result of extensive research, the present inventors have found that unless the amount of alkanolamine contained in the aqueous solution of aliphatic quaternary ammonium hydroxide to be replenished is taken into consideration, the composition of the treatment liquid (stripper composition) will not be properly maintained, and the removability (stripping ability) of the resin mask may decrease. Therefore, in one or more embodiments, the present disclosure is based on the finding that when a processing liquid (an alkaline stripper composition containing carbonate ions) (Liquid C) after use in substrate processing is replenished with an aqueous solution (Liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine, the amount of aliphatic quaternary ammonium hydroxide consumed for neutralizing carbon dioxide is calculated from the carbon dioxide concentration in the processing liquid after use in substrate processing, and the amount of alkanolamine contained in Liquid A that corresponds to the amount of aliphatic quaternary ammonium hydroxide is calculated as a new index to prepare a recycled processing liquid, thereby improving the peelability (removability) of the resin mask.

[0016] That is, in one aspect, the present disclosure relates to an analytical system (hereinafter also referred to as "the analytical system of the present disclosure") including: a carbonate concentration determination unit that determines the concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained after treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in liquid C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in liquid A, which contains an aliphatic quaternary ammonium hydroxide in the same amount as the aliphatic quaternary ammonium hydroxide consumed for neutralizing the carbon dioxide in liquid C. In another aspect, the present disclosure relates to an analytical system (hereinafter also referred to as "the analytical system of the present disclosure") including: a carbonate concentration determination unit that determines the concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained after treating a substrate having a resin mask with a treatment liquid obtained by using a mixture of an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine and an aqueous solution (liquid B) containing an organic solvent and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in liquid C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in liquid A, which contains an aliphatic quaternary ammonium hydroxide in the same amount as the aliphatic quaternary ammonium hydroxide consumed for neutralizing the carbon dioxide in liquid C.

[0017] According to one or more embodiments of the present disclosure, an analytical system using a new index for preparing a reused treatment liquid can be provided. The analytical system of the present disclosure allows the preparation of a reused treatment liquid taking into account the amount of alkanolamine contained in Liquid A to be replenished to Liquid C. This improves the resin mask removability (stripping ability) of the circulated treatment liquid, thereby enabling the production of high-quality electronic components with a high yield.

[0018] In the present disclosure, a resin mask is a mask for protecting the surface of a material from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask may be a resist layer after exposure and development processes, a resist layer that has been subjected to at least one of exposure and development processes (hereinafter also referred to as "exposed and / or developed"), or a hardened resist layer. In one or more embodiments, the resin mask is formed using a resist whose physical properties, such as solubility in a developer, change when exposed to light, an electron beam, or the like. Resists are broadly classified into negative and positive types based on how they react with light or an electron beam. Negative resists have the property of decreasing their solubility in a developer when exposed to light, and the exposed portion of a layer containing negative resist (hereinafter also referred to as a "negative resist layer") is used as a resin mask after exposure and development. Positive resists have the property of increasing their solubility in a developer when exposed to light, and the exposed portion of a layer containing positive resist (hereinafter also referred to as a "positive resist layer") is removed after exposure and development, and the unexposed portion is used as a resin mask. By using a resin mask with such properties, fine connections on a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed. In one or more embodiments, the resin material for forming the resin mask may be a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film may be used.

[0019] <Carbonated concentration determination unit> In one or more embodiments, the carbonate concentration determining unit determines the concentration of carbonate ions (carbonate concentration) in the processing liquid (liquid C) after processing the substrate having the resin mask. In one or more embodiments, the carbonate concentration determination unit includes a titration unit that titrates solution C, and a calculation unit that calculates the carbonate concentration in solution C from the titration result of solution C. Examples of the titration method include potentiometric titration. In one or more embodiments, the calculation unit may be a calculation unit that calculates the carbon dioxide concentration in Solution C using artificial intelligence (AI) that has been trained by machine learning based on training data from titrations in advance. In one or more embodiments, the carbonate concentration determination unit may include a calculation unit that calculates the carbonate concentration in the solution C from the number of substrates processed, using data indicating the relationship between the time required to process one substrate and the increase in carbonate concentration per unit time, which data has been prepared in advance.

[0020] (Carbonate in liquid C) In one or more embodiments of the present disclosure, the carbon dioxide concentration (content) in the solution C is determined by the carbon dioxide concentration determining unit as described above. In one or more embodiments, the liquid C in the present disclosure is a processing liquid (removal agent composition) that contains carbon dioxide (carbonate ions) as a result of carbon dioxide gas being dissolved in the processing liquid during substrate processing or circulation. In one or more embodiments, the carbonic acid (carbonate ions) contained in the processing liquid (liquid C) after use in substrate processing is derived from carbon dioxide gas in the air, etc. In general, from the viewpoint of improving the peelability (removability) of the resin mask, it is preferable that the carbonate concentration (content) in Solution C is as low as possible. For example, from the viewpoint of improving the peelability (removability) of the resin mask, the carbonate concentration (content) in the treatment solution is preferably 10 mol / L or less, more preferably 5 mol / L or less, and even more preferably 1 mol / L or less, and is 0.1 mol / L or more.

[0021] The molar ratio of aliphatic quaternary ammonium hydroxide to carbonate ion in the solution C (aliphatic quaternary ammonium hydroxide / carbonate ion) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more, from the viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, is preferably 100 or less, more preferably 30 or less, and even more preferably 10 or less. More specifically, the molar ratio (aliphatic quaternary ammonium hydroxide / carbonate ion) in the solution C is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 30 or less, and even more preferably 1 or more and 10 or less.

[0022] <Alkanolamine concentration determination unit> In one or more embodiments, the alkanolamine concentration determination unit determines the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, based on the carbon dioxide concentration in Solution C determined by the carbon dioxide concentration determination unit. In one or more embodiments, this amount of alkanolamine can also be referred to as the amount of alkanolamine brought in from Solution A to neutralize carbon dioxide in Solution C. The unit of this amount of alkanolamine may be concentration or mass. As described below, this amount of alkanolamine can be used when preparing a recycled treatment solution from used Solution C.

[0023] In one or more embodiments, the alkanolamine concentration determining unit determines the amount of the alkanolamine using the following formula (I): Amount of alkanolamine (mass%) = [carbonate concentration in solution C (mol / L) × C × molar mass of aliphatic quaternary ammonium hydroxide (g / mol)] ÷ amount of aliphatic quaternary ammonium hydroxide in solution A (mass%) × amount of alkanolamine in solution A (mass%) (I) In the above formula (I), the coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralizations added, and the unit conversion coefficient, and is a value in the range of 0.01 to 1. In one or more embodiments, the coefficient C is defined as the degree of neutralization × the number of neutralized ions × the unit conversion coefficient. In one or more embodiments, the coefficient C is the number of aliphatic quaternary ammonium ions added to carbonate ions, and can be determined by the valences of the carbonate and the aliphatic quaternary ammonium hydroxide. In one or more embodiments, the degree of neutralization is 0 to 1, and can usually be 1. The neutralization addition number is the acid valence divided by the alkali valence of the aliphatic quaternary ammonium hydroxide, and in one or more embodiments, it is 0 to 5, and can usually be 2. The unit conversion factor, for example, when converting g / L to mass %, is 0.1. For example, when the aliphatic quaternary ammonium hydroxide is TMAH, the degree of neutralization is 1, the number of neutralization additions is 2, and the unit conversion coefficient (when converting g / L to mass%) is 0.1, and the coefficient C = 0.2 can be used in formula (I).

[0024] [Substrate processing system] In one aspect, the present disclosure relates to a substrate processing system (hereinafter also referred to as "the substrate processing system of the present disclosure") that includes a substrate processing apparatus that processes a substrate having a resin mask using a processing liquid obtained by using an aqueous solution (Liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine, an analysis system of the present disclosure, and a reuse processing liquid production unit that replenishes the processing liquid (Liquid C) after processing the substrate having the resin mask with a replenisher based on the amount of alkanolamine determined by the analysis system, to produce a reuse processing liquid for use in the substrate processing apparatus.

[0025] Hereinafter, an embodiment of a substrate processing system according to the present disclosure will be described with reference to the drawings. The example described below illustrates one embodiment of the substrate processing system of the present disclosure, and the components, their placement and connection configuration, etc., do not limit the scope of the claims unless otherwise stated in the claims. Furthermore, among the components described below, any components that are not described in an independent claim that represents the highest concept of the present disclosure will be described as optional components. Furthermore, in the description of the operations, the order of steps may be changed or known steps may be added as necessary.

[0026] One embodiment of a substrate processing system of the present disclosure is shown in FIG. The substrate processing system shown in FIG. 1 includes a substrate processing apparatus 10, an analysis system 20, a reuse processing liquid production unit 30, and a control unit 40.

[0027] <Substrate processing equipment> In one or more embodiments, the substrate processing apparatus 10 includes a processing liquid tank 11 and a processing section 12, as shown in FIG.

[0028] The processing liquid tank 11 stores the processing liquid. In one or more embodiments, the treatment liquid stored in the treatment liquid tank 11 may be a treatment liquid obtained using an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine (liquid A), a treatment liquid obtained using a mixture of an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine (liquid A) and an aqueous solution containing an organic solvent and an alkanolamine (liquid B), or a recycled treatment liquid. Details of liquid A, liquid B, the treatment liquid, and the recycled treatment liquid will be described later.

[0029] The processing section 12 processes a substrate (object to be processed) having a resin mask thereon using the processing liquid supplied from the processing liquid tank 11. The object to be processed will be described later. In one or more embodiments, the processing includes cleaning the substrate having the resin mask, stripping the resin mask from the substrate having the resin mask, and removing the resin mask from the substrate having the resin mask. In one or more embodiments, the treatment includes contacting a treatment liquid with the object to be treated.

[0030] In the processing section 12, examples of a method for cleaning a substrate having a resin mask using a processing liquid, a method for peeling off a resin mask from an object to be processed using a processing liquid, or a method for bringing the processing liquid into contact with an object to be processed include a method for bringing the object into contact by immersing the object in a cleaning bath containing the processing liquid, a method for bringing the object into contact by spraying the processing liquid (shower method), and an ultrasonic cleaning method for irradiating the object with ultrasonic waves while the object is immersed in the processing liquid. In one or more embodiments, the processing unit 12 uses the processing liquid supplied from the processing liquid tank 11 for processing (cleaning) as is without diluting it. For example, in one or more embodiments, the processing unit 12 sprays the processing liquid onto a substrate (object to be processed) having a resin mask. The time for which the treatment solution is brought into contact with or immersed in the treatment object (contact time or immersion time) may be, for example, from 1 minute to 10 minutes, and further from 2 minutes to 6 minutes. When the treatment liquid is sprayed and brought into contact, the spray time may be, for example, from 1 minute to 10 minutes, and further from 2 minutes to 6 minutes.

[0031] In order to facilitate the exertion of the peeling and cleaning power (resin mask peeling ability and resin mask removal ability) of the treatment liquid, it is preferable to irradiate the treatment liquid with ultrasonic waves when the treatment liquid comes into contact with the treatment object, and it is more preferable that the ultrasonic waves have a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are, for example, preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0032] The temperature (processing temperature) of the processing solution used in processing unit 12 is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of easily exerting the peeling and cleaning power (resin mask peeling ability, resin mask removal ability) of the processing solution, and is preferably 70°C or lower, more preferably 60°C or lower, from the viewpoint of reducing the impact on the substrate.

[0033] At least a portion of the processing liquid (liquid C) after being used for processing in the processing unit 12 is recovered and stored again in the processing liquid tank 11. In this way, the processing liquid in the processing liquid tank 11 is recycled and reused.

[0034] In one or more embodiments, the substrate processing apparatus 10 may include a cleaning unit that rinses the substrate with water after processing in the processing unit 12, and a drying unit that dries the substrate after rinsing with water. An example of a rinsing method is running water rinsing. An example of a drying method is air blow drying. In one or more embodiments, the substrate processing apparatus 10 may include a cleaning section that rinses the substrate with water after processing in the processing section 12 .

[0035] <Analysis system> The analysis system 20 shown in FIG. 1 has a carbon dioxide concentration determiner 21 and an alkanolamine concentration determiner 22. The carbon dioxide concentration determination unit 21 determines the carbon dioxide concentration in the processing liquid (liquid C) after use in the substrate processing apparatus 10. The carbon dioxide concentration can be determined in the same manner as in the carbon dioxide concentration determination unit in the analysis system of the present disclosure described above. Alkanolamine concentration determination unit 22 determines the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed for neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in Solution C determined by carbon dioxide concentration determination unit 21. The alkanolamine concentration can be determined in the same manner as in the alkanolamine concentration determination unit in the above-described analysis system of the present disclosure. The carbon dioxide concentration determining section and the alkanolamine concentration determining section may be integrated into one unit or may be separate units.

[0036] <Reused Processing Liquid Manufacturing Department> The reuse processing liquid producing section 30 replenishes the liquid C with the replenisher liquid based on the amount of alkanolamine determined by the analysis system 20 to prepare a reuse processing liquid for use in the substrate processing apparatus 10. In one or more embodiments, the replenisher is an aqueous solution (solution A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine and / or an aqueous solution (solution B) containing an organic solvent and an alkanolamine. Methods for replenishing the replenisher liquid to prepare a reused processing liquid include a method of mixing liquid A with liquid C, a method of mixing liquid B with liquid C, and a method of mixing liquid A, liquid B, and liquid C. Known methods can be used as the mixing method. In one or more embodiments, the mixing conditions (the mixing ratio of liquid A and liquid C, the mixing ratio of liquid B and liquid C, and the mixing ratio of liquid A, liquid B, and liquid C) are set based on the amount of alkanolamine determined by the analysis system 20.

[0037] <Control unit> The control unit 40 controls the supply amount of the replenisher liquid (liquid A and / or liquid B) to be replenished to liquid C based on the amount of alkanolamine determined by the analysis system 20. In one or more embodiments, the control unit 40 may be a control unit that determines the mixing ratio of liquid A and liquid C, the mixing ratio of liquid B and liquid C, or the mixing ratio of liquid A, liquid B, and liquid C (mixing conditions) based on the amount of alkanolamine determined by the analysis system 20, and controls the supply amount of liquid A or liquid B to be replenished in the reuse treatment liquid production unit 30. In one or more embodiments, the control unit 40 may determine the mixing conditions (the mixing ratio of liquid A and liquid C, the mixing ratio of liquid B and liquid C, and the mixing ratio of liquid A, liquid B, and liquid C) so as to minimize the sum of the differences between the target concentrations of the amine, aliphatic quaternary ammonium hydroxide, and organic solvent in the alkanolamine after mixing. In one or more embodiments, the control unit 40 may be a control unit that controls the reused processing liquid producing unit 30 to mix the liquid A and the liquid C at a ratio between the liquid A and the liquid C that is determined by the difference, ratio, and correction coefficient between the amount of alkanolamine in the liquid C after use in the substrate processing apparatus 10 and the amount of alkanolamine determined by the analysis system 20. In one or more embodiments, the control unit 40 may be a control unit that controls the reused processing liquid producing unit 30 so as to mix the liquid B containing the amount of monoethanolamine obtained by subtracting the amount of alkanolamine determined by the analysis system 20 from the difference between the target concentration of alkanolamine and the concentration of the liquid C after use in the substrate processing apparatus 10.

[0038] In one or more embodiments, the control unit 40 may control the substrate processing apparatus 10 to change at least one selected from the time for which the processing liquid is in contact with or immersed in the workpiece and the temperature of the processing liquid during use, based on the amount of alkanolamine determined by the analysis system 20.

[0039] In one or more embodiments, the control unit 40 may control the replenishment of the processing liquid tank 11 with the processing liquid based on the remaining amount of the processing liquid in the processing liquid tank 11. The replenishment of the processing liquid includes the supply of a processing liquid obtained using liquid A, the supply of a processing liquid obtained using a mixture of liquid A and liquid B, and the supply of a recycled processing liquid.

[0040] The configuration of the substrate processing system shown in FIG. 1 described above is an example and is not limited to this example. For example, in FIG. 1, the control unit 40 is provided outside the substrate processing apparatus 10 and the analysis system 20, but the control unit 40 may be provided inside the substrate processing apparatus 10 or may be provided inside the analysis system 20.

[0041] [Operation] FIG. 2 is a flowchart showing an example of the operation of the analysis system 20 in the substrate processing system of the present disclosure. The operation of the analysis system may not be interpreted as being limited to FIG. 2. First, the carbonic acid concentration determination unit 21 titrates the solution C after being used for substrate processing (step S1) and determines the carbonate ion concentration in the solution C (step S2). Next, the alkanolamine concentration determination unit 22 determines the amount of alkanolamine contained in the solution A containing the same amount of aliphatic quaternary ammonium hydroxide as that consumed for neutralization of carbonic acid from the carbonic acid concentration in the solution C determined by the carbonic acid concentration determination unit 21 (step S3). Then, the determined amount of alkanolamine is transmitted to the control unit 40. Note that the substrate processing in the substrate processing apparatus 10 may be continuously performed during the operations of steps S1 to S3.

[0042] <Solution A> Solution A is an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine, and in one or more embodiments, contains optional components (other components described later) as necessary. In one or more embodiments, solution A can be obtained by blending an aliphatic quaternary ammonium hydroxide, an alkanolamine, water, and optional components (other components described later) as necessary by a known method. Here, "blending" includes mixing an aliphatic quaternary ammonium hydroxide, an alkanolamine, water, and optional components (other components described later) simultaneously or in any order. As a method for preparing Solution A, an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine may be obtained, or an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine may be prepared by oneself. In one or more embodiments, the liquid A is a replenisher liquid for replenishing the stripper composition component of the processing liquid (liquid C) that has become low due to use.

[0043] (Aliphatic quaternary ammonium hydroxide in solution A) Examples of the aliphatic quaternary ammonium hydroxide contained in Solution A include quaternary ammonium hydroxides represented by the following formula (II): The aliphatic quaternary ammonium hydroxides may be one type or a combination of two or more types. [ka] In the above formula (II), R 4 , R 5 , R 6 and R 7 are each independently at least one selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. The quaternary ammonium hydroxide represented by formula (II) is a salt consisting of a quaternary ammonium cation and hydroxide, and examples thereof include at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, tetramethylammonium hydroxide (TMAH) is preferred from the viewpoint of improving the peelability (removability) of the resin mask. From the viewpoint of improving the peelability (removability) of the resin mask, the content of the aliphatic quaternary ammonium hydroxide in Solution A is preferably 2% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. More specifically, the content of the aliphatic quaternary ammonium hydroxide in Solution A is preferably 2% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less. When two or more types of aliphatic quaternary ammonium hydroxides are combined, the content of the aliphatic quaternary ammonium hydroxide in Solution A is the total content of these.

[0044] (Alkanolamine in solution A) Examples of the alkanolamine (amino alcohol) contained in Solution A include compounds represented by the following formula (I): The alkanolamine may be one type, or two or more types may be combined. [ka] In the above formula (I), R 1 represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group, and R 2 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group, and R 3 represents a hydroxyethyl group or a hydroxypropyl group. Examples of component A include at least one selected from monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, and N-(β-aminoethyl)diisopropanolamine. Among these, monoethanolamine (MEA) is preferred from the viewpoint of improving the peelability (removability) of the resin mask. When Solution A contains an alkanolamine, the content of the alkanolamine in Solution A is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of improving the peelability (removability) of the resin mask. From the viewpoint of improving the peelability (removability) of the resin mask and preventing substrate damage, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 50% by mass or less. More specifically, the content of the alkanolamine in Solution A is preferably 0.1% by mass or more and 80% by mass or less, more preferably 1% by mass or more and 75% by mass or less, and even more preferably 3% by mass or more and 50% by mass or less. When two or more alkanolamines are used in combination, the content of the alkanolamines in Solution A is the total content of the alkanolamines.

[0045] (Water in Solution A) From the viewpoint of improving the peelability (removability) of the resin mask, the water content in Solution A is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, and from the same viewpoint, it is preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. More specifically, the water content in Solution A is preferably 10% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 85% by mass or less, and even more preferably 50% by mass or more and 80% by mass or less.

[0046] (Other ingredients in Solution A) In one or more embodiments, Solution A may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents, such as alkaline agents other than the above-mentioned alkanolamines and aliphatic quaternary ammonium hydroxides, amines other than the above-mentioned alkanolamines, organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents. In one or more embodiments, Solution A does not contain an inhibitor. For example, the content of the inhibitor in Solution A is preferably less than 0.05% by mass, more preferably 0.01% by mass or less, and even more preferably 0% by mass (i.e., no inhibitor is contained). In one or more embodiments, it is preferable that the liquid A substantially does not contain carbonic acid. For example, from the viewpoint of improving the resin mask peelability (removability), the carbonic acid concentration (content) in the liquid A is preferably 1 mol / L or less, more preferably 0.5 mol / L or less, and still more preferably 0.2 mol / L or less.

[0047] <Liquid B> In one or more embodiments, the liquid B is an aqueous solution containing an organic solvent and an alkanolamine, and may further contain optional components (inhibitor, alkali metal hydroxide, other components) described later as necessary. In one or more embodiments, the liquid B can be obtained by blending an organic solvent, an alkanolamine, water, and optional components (inhibitor, alkali metal hydroxide, other components) described later as necessary by a known method. Here, "blending" includes mixing an organic solvent, an alkanolamine, water, and optional components (inhibitor, alkali metal hydroxide, other components) described later as necessary simultaneously or in any order. As a method for preparing the liquid B, an aqueous solution containing an organic solvent and an alkanolamine may be obtained, or an aqueous solution containing an organic solvent and an alkanolamine may be prepared by oneself. In one or more embodiments, the liquid B is a replenishing liquid for replenishing the stripper composition components of the processing liquid (liquid C) that has decreased during use.

[0048] (Organic solvent in liquid B) As the organic solvent contained in the liquid B, from the viewpoint of improving the resin mask peelability (removability), preferably a ketone or an alcohol compound, more preferably a glycol ether, and still more preferably butyl diglycol (BDG) can be mentioned. The organic solvent may be one kind or a combination of two or more kinds. When Liquid B contains an organic solvent, the content of the organic solvent in Liquid B is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, from the viewpoints of stability and miscibility, and from the same viewpoints, is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. More specifically, the content of the organic solvent in Liquid B is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less. When two or more organic solvents are used in combination, the content of the organic solvent in Liquid B refers to the total content of the organic solvents.

[0049] (Alkanolamine in solution B) Examples of the alkanolamine contained in the solution B include the alkanolamine contained in the solution A described above. From the viewpoints of stability and miscibility, the content of alkanolamine in Solution B is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more. From the same viewpoints, it is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. More specifically, the content of alkanolamine in Solution B is preferably 15% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less, and even more preferably 35% by mass or more and 50% by mass or less. When two or more alkanolamines are used in combination, the content of alkanolamine in Solution B is the total content of these alkanolamines.

[0050] (Water in Solution B) Examples of water contained in the solution B include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water. From the viewpoints of stability and miscibility, the water content in Solution B is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and from the same viewpoints, it is preferably 70% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less. More specifically, the water content in Solution B is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 15% by mass or more and 20% by mass or less.

[0051] (Inhibitor in solution B) In one or more embodiments, Solution B may further contain an inhibitor. Examples of inhibitors contained in Solution B include compounds containing heteroatoms, specifically compounds containing nitrogen atoms, sulfur atoms, and oxygen atoms. More specifically, azoles are used, and even more specifically, at least one selected from pyrazole, methylpyrazole, thiazole, oxazole, triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, tetrazole, triazine, tetrazine, pentazole, imidazole, methylimidazole, phenylimidazole, and dimethylbenzimidazole is used. Among these, from the viewpoint of improving the peelability (removability) of the resin mask, the inhibitor is preferably at least one selected from triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, imidazole, and dimethylbenzimidazole, and more preferably at least one selected from benzotriazole, imidazole, and dimethylbenzimidazole. The inhibitor may be one type or a combination of two or more types. From the viewpoint of etching suppression, the content of the inhibitor in Solution B is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. From the same viewpoint, it is preferably 6% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less. More specifically, the content of the inhibitor in Solution B is preferably 0.05% by mass or more and 6% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less. When two or more inhibitors are used in combination, the content of the inhibitor in Solution B is the total content of the inhibitors.

[0052] (Alkali metal hydroxide in solution B) In one or more embodiments, Solution B may further contain an alkali metal hydroxide. From the viewpoint of improving the peelability (removability) of the resin mask, the alkali metal hydroxide contained in Solution B is preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, more preferably at least one of sodium hydroxide and potassium hydroxide, and even more preferably potassium hydroxide. The alkali metal hydroxide may be one type or a combination of two or more types. When Solution B contains an alkali metal hydroxide, the content of the alkali metal hydroxide in Solution B is preferably 0.3% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoints of stability and miscibility, and from the same viewpoints, is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of the alkali metal hydroxide in Solution B is preferably 0.3% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less. When two or more alkali metal hydroxides are used in combination, the content of the alkali metal hydroxides in Solution B refers to the total content of these.

[0053] (Other ingredients in solution B) In one or more embodiments, Solution B may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents, such as alkaline agents other than the above-mentioned alkanolamines and alkali metal hydroxides, amines other than the above-mentioned alkanolamines, organic solvents other than the above-mentioned organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents. In one or more embodiments, it is preferable that Solution B be substantially free of carbon dioxide. For example, from the viewpoint of improving the peelability (removability) of the resin mask, the concentration (content) of carbon dioxide in Solution B is preferably 1 mol / L or less, more preferably 0.5 mol / L or less, and even more preferably 0.2 mol / L or less.

[0054] <Processing liquid> In one or more embodiments, the treatment liquid can be obtained using liquid A, and contains, for example, an aliphatic quaternary ammonium, an alkanolamine, water, and, as necessary, optional components described below (inhibitor, alkali metal hydroxide, organic solvent, and other components). In one or more other embodiments, the treatment liquid is a mixed liquid obtained by mixing liquid A and liquid B, and contains, for example, an aliphatic quaternary ammonium, an alkanolamine, an organic solvent, water, and optional components described below (inhibitor, alkali metal hydroxide, other components) as needed. In one or more embodiments, the treatment liquid can be obtained by blending an aliphatic quaternary ammonium, an alkanolamine, water, and, if necessary, optional components described below (inhibitor, alkali metal hydroxide, organic solvent, other components) by a known method. Here, "blending" includes mixing the alkanolamine, water, and, if necessary, optional components described below (inhibitor, alkali metal hydroxide, organic solvent, other components) simultaneously or in any order. The mixing method can be a known method, and the mixing conditions may be set appropriately.

[0055] In one or more embodiments, the treatment liquid is a treatment liquid for use in treating a substrate having a resin mask, a cleaning composition for stripping a resin mask for cleaning a substrate having a resin mask, or a stripper composition for stripping a resin mask from a substrate having a resin mask.

[0056] (Aliphatic quaternary ammonium hydroxide in the treatment solution) Examples of the aliphatic quaternary ammonium hydroxide contained in the treatment liquid include the aliphatic quaternary ammonium hydroxide contained in the above-mentioned liquid A. From the viewpoint of improving the peelability (removability) of the resin mask, the content of the aliphatic quaternary ammonium hydroxide in the treatment liquid is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and even more preferably 3% by mass or more. From the same viewpoint, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. More specifically, the content of the aliphatic quaternary ammonium hydroxide in the treatment liquid is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and even more preferably 3% by mass or more and 7% by mass or less. When two or more types of aliphatic quaternary ammonium hydroxides are combined, the content of the aliphatic quaternary ammonium hydroxide in the treatment liquid refers to the total content thereof.

[0057] (Alkanolamine in processing solution) Examples of the alkanolamine contained in the treatment liquid include the aliphatic alkanolamine contained in the above-mentioned liquid A. From the viewpoint of improving the peelability (removability) of the resin mask, the content of the alkanolamine in the treatment liquid is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. From the same viewpoint, it is preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. More specifically, the content of the alkanolamine in the treatment liquid is preferably 3% by mass or more and 18% by mass or less, preferably 5% by mass or more and 15% by mass or less, and more preferably 8% by mass or more and 12% by mass or less. When two or more alkanolamines are used in combination, the content of the alkanolamines in the treatment liquid is the total content of the alkanolamines.

[0058] (Water in the treatment solution) The water content in the treatment liquid can be the remainder obtained by subtracting the above-mentioned components (aliphatic quaternary ammonium salt, alkanolamine, organic solvent, inhibitor, alkali metal hydroxide, and other components) from the entire treatment liquid. Specifically, from the viewpoint of improving the peelability (removability) of the resin mask, the water content in the treatment liquid is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and from the same viewpoint, is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0059] (organic solvent in processing solution) Examples of the organic solvent contained in the treatment liquid include the organic solvents contained in the above-mentioned liquid B. When the treatment liquid contains an organic solvent, the content of the organic solvent in the treatment liquid is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. More specifically, the content of the organic solvent in the treatment liquid is preferably 2% by mass or more and 25% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 15% by mass or less. When two or more organic solvents are used in combination, the content of the organic solvent in the treatment liquid refers to the total content of the organic solvents.

[0060] (Inhibitors in processing solution) Examples of the inhibitor contained in the treatment liquid include the inhibitors contained in the above-mentioned liquid B. When the treatment solution contains an inhibitor, the content of the inhibitor in the treatment solution is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more, from the viewpoint of etching suppression. From the same viewpoint, the content of the inhibitor in the treatment solution is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. More specifically, the content of the inhibitor in the treatment solution is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.02% by mass or more and 1% by mass or less, and even more preferably 0.05% by mass or more and 0.5% by mass or less. When two or more inhibitors are used in combination, the content of the inhibitor in the treatment solution is the total content of the inhibitors.

[0061] (Alkali metal hydroxide in the treatment solution) Examples of the alkali metal hydroxide contained in the treatment liquid include the alkali metal hydroxide contained in the above-mentioned liquid B. When the treatment liquid contains an alkali metal hydroxide, the content of the alkali metal hydroxide in the treatment liquid is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of improving the peelability (removability) of the resin mask. From the same viewpoint, it is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less. More specifically, the content of the alkali metal hydroxide in the treatment liquid is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 2% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less. When two or more alkali metal hydroxides are used in combination, the content of the alkali metal hydroxides in the treatment liquid refers to the total content of the alkali metal hydroxides.

[0062] (Other components in the processing solution) In one or more embodiments, the treatment liquid may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents (strippers), such as alkaline agents other than the above-mentioned alkanolamines and alkali metal hydroxides, amines other than the above-mentioned alkanolamines, organic solvents other than the above-mentioned organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents.

[0063] In the present disclosure, the "content of each component in the treatment liquid" refers to the content of each component at the time of use, i.e., at the time when the treatment liquid is first used for substrate treatment (resin mask stripping treatment). In one or more embodiments, the content of each component in the treatment liquid in the present disclosure can be considered to be the blending amount of each component in the treatment liquid.

[0064] (pH of treatment solution) From the viewpoint of improving the peelability (removability) of the resin mask, the pH of the treatment liquid is preferably 10 or more, more preferably 11 or more, and even more preferably 12 or more, and from the viewpoint of suppressing damage to the substrate resin, the pH is preferably 15 or less, more preferably 14.7 or less, and even more preferably 14.5 or less. In the present disclosure, the pH of the treatment liquid is a value at 25°C, and can be measured using a pH meter, specifically, by the method described in the Examples.

[0065] <Item to be processed> In one or more embodiments, the workpiece is a substrate having a resin mask. Examples of the substrate include a printed circuit board, a wafer, a copper plate, and an aluminum plate. The resin mask may be, for example, a negative resin mask or a positive resin mask, and a negative resin mask is preferred in terms of the ease with which the effects of the present disclosure can be exerted. Examples of negative resin masks include negative dry film resists that have been exposed and / or developed. In the present disclosure, a negative resin mask is formed using a negative resist, and examples thereof include a negative resist layer that has been subjected to exposure and / or development treatment. In the present disclosure, a positive resin mask is formed using a positive resist, and examples thereof include a positive resist layer that has been subjected to exposure and / or development treatment. The thickness of the resin mask is, for example, 5 μm to 35 μm or less.

[0066] In one or more embodiments, the substrate (processing object) having a resin mask may be a substrate having a metal layer and a resin mask on its surface. In one or more embodiments, the metal layer is a copper plating layer, which can be formed by, for example, copper electroplating. The thickness of the metal layer is, for example, 3 μm or more and 30 μm or less. In one or more embodiments, the metal layer is used as a metal wiring or a wiring connection portion. In one or more embodiments, the resin mask may be a resin mask (resin mask layer) present in the form of perforations in a metal layer (see FIG. 1). In one or more embodiments, the sides of the resin mask are surrounded by a metal layer. In one or more embodiments, the shape of the resin mask layer may be a polygonal (e.g., square, hexagonal, octagonal) columnar, cylindrical, or approximately cylindrical shape. The diameter of the resin mask layer (the diameter of the circumscribed circle in the case of a polygonal shape) may be, for example, 20 μm or more and 200 μm or less. The thickness of the resin mask layer may be, for example, 5 μm or more and 50 μm or less. The interface ratio of the resin mask present in the perforation (μm - ) (=Interface line length between resin mask and metal layer (μm) / Area of ​​resin mask (μm 2 )) may be 0.01 or more and 0.5 or less, or 0.02 or more and 0.2 or less. Here, the interface line length between the resin mask and the metal layer is, for example, the length of the circumference when the resin mask is circular when viewed from above. A new problem has been found in that conventional strippers have poor strippability when used on a workpiece having a resin mask with such a structure. In one or more embodiments, the treatment liquid used in step 1 and the recycled treatment liquid described below can effectively strip a resin mask with such a structure. In one or more embodiments, the workpiece according to the present disclosure may be an object having at least one resin mask attached to a metal layer in the form of perforations, as described above.

[0067] In one or more embodiments, the substrate (processing object) having a resin mask may be a substrate having a metal layer and a resin mask on its surface. In one or more embodiments, the metal layer is a copper plating layer, which can be formed by, for example, copper electroplating. The thickness of the metal layer is, for example, 3 μm or more and 30 μm or less. In one or more embodiments, the metal layer is used as a metal wiring or a wiring connection portion.

[0068] In one or more other embodiments, the substrate (workpiece) having the resin mask may be, for example, an electronic component having a metal layer and a resin mask on its surface, or a manufacturing intermediate thereof. Examples of the electronic component include at least one component selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. The manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, and includes an intermediate product after resin mask treatment. Specific examples of the workpiece include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate by undergoing at least one of soldering using a resin mask and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.). In this disclosure, soldering refers to applying solder to the resin mask-free areas of the substrate and forming solder bumps by heating. In this disclosure, plating refers to performing at least one plating process selected from copper plating, aluminum plating, nickel plating, and tin plating on the resin mask-free areas of the substrate. The resin mask-free areas refer to areas in a resist pattern (patterned resin mask) formed by developing a resin mask laminated to a substrate, where the resin mask has been removed by the developing process.

[0069] In one or more other embodiments, the substrate (processed object) having the resin mask may be a substrate having a resin mask in a fine gap. For example, the substrate having a resin mask in a fine gap may be a substrate on which a non-cured resin mask is applied to the surface of the substrate by at least one of exposure and development, and then the non-cured resin mask is removed and a circuit pattern is formed by plating. The non-plated portions of the formed circuit pattern have a cured resin mask. In the present disclosure, in one or more embodiments, a gap refers to the distance between circuit patterns (thin line portions) (the spacing between adjacent thin line portions), and is also called a space (S). The thickness (plating thickness) of the thin line portions is, for example, 3 μm or more and 30 μm or less. The width of the thin line portion is also called a line (L). In one or more embodiments, a resin mask in a fine gap refers to a resin mask that exists in a space with a space width (S) of 10 μm or less. The thickness of the resin mask is, for example, 5 μm or more and 35 μm or less. An example of a resin mask in a fine gap is a resin mask that exists in a space with a space width (S) of 4 to 7 μm.

[0070] <Recycled processing liquid> In one or more embodiments, the recycled treatment liquid is produced in the recycled treatment liquid production unit. In one or more embodiments, the recycled treatment liquid is a mixed liquid obtained by mixing liquid A and liquid C, and in one or more other embodiments, it is a mixed liquid obtained by mixing liquid A, liquid B, and liquid C. The components contained in the recycled treatment liquid include the same components as those in the treatment liquid described above. The preferred content of each component contained in the recycled treatment liquid is the same as the preferred content of each component contained in the treatment liquid described above. In one or more embodiments, the carbonate ions (carbonic acid) contained in the recycled treatment liquid are derived from carbon dioxide gas in the air, etc. Generally, the carbon dioxide concentration (content) in the recycled treatment liquid is preferably as low as possible from the viewpoint of improving the peelability (removability) of the resin mask. For example, from the viewpoint of improving the peelability (removability) of the resin mask, the carbon dioxide concentration (content) in the recycled treatment liquid is preferably 10 mol / L or less, more preferably 5 mol / L or less, even more preferably 1.1 mol / L or less, and even more preferably 1 mol / L or less, and 0.1 mol / L or more.

[0071] [Removal method] In one aspect, the present disclosure relates to a method for stripping a resin mask (hereinafter also referred to as the "stripping method of the present disclosure"), which includes using a substrate processing system of the present disclosure to strip a resin mask from a substrate (workpiece) having the resin mask. Examples of the object to be treated in the peeling method of the present disclosure include the above-mentioned object to be treated. According to the peeling method of the present disclosure, by using the substrate processing system of the present disclosure, it is possible to provide a resin mask peeling method that is excellent in resin mask removability (peeling ability).

[0072] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for manufacturing an electronic component, including the resin mask stripping method of the present disclosure. The electronic component may be, for example, at least one component selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. According to the method for manufacturing electronic components disclosed herein, by using the resin mask stripping method disclosed herein, the resin mask stripping property (removability) of the circulating treatment liquid can be improved, so that the resin mask adhered to the substrate can be effectively removed, enabling the manufacturing of highly reliable electronic components. [Example]

[0073] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0074] Example 1 1. Preparation of post-use processing solution (solution C) Solution D shown in Table 1 was obtained by mixing alkanolamine (MEA), a carbonate source (ammonium carbonate), and water. The carbonate source in Solution D, ammonium carbonate, generates carbonate ions in aqueous solution. The carbonic acid in Solution D shown in Table 1 represents carbonate ions generated from ammonium carbonate. Aliphatic quaternary ammonium hydroxide (TMAH), alkanolamine (MEA), and water were mixed to obtain Solution A shown in Table 1. Liquid D and Liquid A were mixed for 1 hour at the mixing ratio shown in Table 1 to obtain Liquid C (used processing liquid) (pH: 11.9) shown in Table 1. In Liquid C, a portion of the TMAH reacts with carbonate (ions) to form a neutralized salt. Liquid C containing this neutralized salt is intended to represent the processing liquid after use in substrate processing in processing section 12 of substrate processing apparatus 10 shown in FIG. The concentrations (amounts) (% by mass or mol / L, active ingredient) of each component in solutions D and A before mixing are shown in Table 1. The concentrations shown in Table 1 are the active ingredient concentrations (% by mass or mol / L) calculated from the amounts mixed.

[0075] The following materials were used to prepare solutions D and A. MEA: Monoethanolamine [Nippon Shokubai Co., Ltd.] Ammonium carbonate [Fujifilm Wako Pure Chemical Industries] (carbonate source) TMAH: Tetramethylammonium hydroxide [Resonac Corporation, 25% aqueous solution] Water [pure water of less than 1 μS / cm produced using the Organo Corporation G-10DSTSET water purification system]

[0076] [pH of treatment solution] The pH of the treatment solution at 25°C was measured using a pH meter (Toa Dempa Kogyo Co., Ltd., HM-30G), and was the value measured 3 minutes after the electrode of the pH meter was immersed in the treatment solution.

[0077] 2. Calculating the amount of alkanolamine using formula (I) From the carbon dioxide concentration in Solution C, the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in Solution C for neutralization of the carbon dioxide, was calculated as follows. First, the carbon dioxide concentration in solution C is calculated using the following formula. Carbonate concentration in solution C (mol / L) = Carbonate concentration of solution C (mol / L) × Mixing ratio of solution C (%) ÷ 100 Next, using the mass ratio of the aliphatic quaternary ammonium hydroxide to the alkanolamine in Solution A, the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide, is calculated from the following formula (I). Amount of alkanolamine (mass%) = [carbonate concentration in solution C (mol / L) × C × molar mass of aliphatic quaternary ammonium hydroxide (g / mol)] ÷ amount of aliphatic quaternary ammonium hydroxide in solution A (mass%) × amount of alkanolamine in solution A (mass%) (I) In the above formula (I), coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralization additions, and a unit conversion coefficient, and is defined as: degree of neutralization (0 to 1, usually 1) × number of neutralization additions (0 to 2, usually 2) × unit conversion coefficient (0.1 when converting g / L to mass%). Here, the degree of neutralization was 1, the number of neutralization additions was 2, and the unit conversion coefficient was 0.1, so coefficient C = 0.2 was used in formula (I).

[0078] 3. Preparation of Recycled Treatment Solution Based on the amount of alkanolamine calculated using formula (I) in 2 above, the mixing ratio of liquid C, liquid A, and liquid B was calculated using the following formula. Based on the calculated mixing ratio, liquid C, liquid A, and liquid B were mixed to prepare a reused treatment liquid. Mixing ratio (mass%) of liquid C used to prepare the recycled treatment liquid = [amount of alkanolamine in liquid C (mass%) - amount of alkanolamine calculated using formula (I) (mass%) ÷ 2.5] ÷ amount of alkanolamine in liquid C (mass%) × 100 Mixing ratio (mass%) of solution A used to prepare the recycled treatment solution = Amount of alkanolamine (mass%) calculated using formula (I) ÷ Amount of alkanolamine in solution A (mass%) ÷ 3.5 × 100 Mixing ratio (mass%) of water used to prepare the reused treatment liquid = 100 - Mixing ratio (mass%) of solution A used to prepare the reused treatment liquid - Mixing ratio (mass%) of solution C used to prepare the reused treatment liquid In the above formula, 2.5 and 3.5 are coefficients set so as to minimize the sum of the differences between the target concentrations of the alkanolamine, the aliphatic quaternary ammonium hydroxide, and the organic solvent after mixing.

[0079] 4. Evaluation of processing liquid Using the prepared recycled treatment liquid of Example 1, the removability (peelability) of the resin mask was evaluated as follows.

[0080] [Test piece for evaluating peelability] The test piece for evaluating peelability was 50 mm x 50 mm in size, and had a 15 μm-thick metal layer 2 formed by copper plating on the surface of a glass epoxy multilayer substrate with a thin copper film, as shown in Figure 3, and a 25 μm-thick resin mask layer 1 made of negative dry film resist in circular areas with a diameter of 300 μm present in the form of perforations in the metal layer 2, with 15 μm of the 25 μm-thick resin mask buried in the metal layer. There were 3,000 perforations. [Resin mask removability (peelability)] 3 kg of the stripping composition was added to a 5-L stainless steel beaker. The beaker was heated to 50°C, and the test pieces were sprayed for 2.5 minutes while circulating the composition using a box-type spray washer equipped with a one-fluid nozzle (full cone type) J020 (Ikeuchi Co., Ltd.) (pressure: 0.05 MPa, spray distance: 8 cm). After rinsing with water for 30 seconds, the test pieces were dried using nitrogen blowing. Using a digital microscope (VHX-6000, Keyence Corporation), the test pieces after the spray treatment were visually observed at 300x magnification to measure the rate of resin mask residue (residue rate). A lower value indicates better resin mask removability (peelability). The results are shown in Table 1.

[0081] [Table 1]

[0082] As shown in Table 1, the recycled treatment liquid prepared in Example 1 exhibited good resin mask stripping properties. [Industrial Applicability]

[0083] According to the present disclosure, an analytical system using a new index for preparing a reused treatment liquid can be provided. Furthermore, by using the analytical system of the present disclosure, it is possible to improve the performance and reliability of manufactured electronic components, thereby improving the productivity of semiconductor devices. [Explanation of symbols]

[0084] 10: Substrate processing equipment 11: Processing liquid tank 12: Processing section 20:Analysis system 21: Carbonate concentration determination unit 22: Alkanolamine concentration determination unit 30: Recycled Processing Liquid Manufacturing Department 40: Control unit 1: Resin mask layer (dry film resist) 2: Metal layer (metal plating layer)

Claims

1. a carbonate concentration determining unit that determines a concentration of carbonate ions (carbonate concentration) in a processing liquid (liquid C) obtained after processing a substrate having a resin mask with a processing liquid containing an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in Solution C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed for neutralizing the carbonate ions in Solution C.

2. a carbonate concentration determining unit that determines a concentration of carbonate ions (carbonate concentration) in a treatment liquid (liquid C) obtained after treating a substrate having a resin mask with a treatment liquid containing a mixture of an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine and an aqueous solution (liquid B) containing an organic solvent and an alkanolamine; and an alkanolamine concentration determination unit that determines, from the carbonate concentration in Solution C determined by the carbonate concentration determination unit, the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed for neutralizing the carbonate ions in Solution C.

3. The analysis system according to claim 1 or 2, wherein the alkanolamine concentration determiner determines the amount of the alkanolamine using the following formula (I): Amount of alkanolamine (mass%) = [carbonate concentration in solution C (mol / L) × C × molar mass of aliphatic quaternary ammonium hydroxide (g / mol)] ÷ amount of aliphatic quaternary ammonium hydroxide in solution A (mass%) × amount of alkanolamine in solution A (mass%) (I) In the above formula (I), the coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralizations added, and the unit conversion coefficient, and is a value in the range of 0.01 to 1.

4. a substrate processing apparatus for processing a substrate having a resin mask using a processing solution containing an aqueous solution (solution A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine; The analysis system according to claim 1 or 2; a recycled processing liquid producing unit that replenishes the processing liquid (liquid C) with a replenisher after processing the substrate having the resin mask based on the amount of alkanolamine determined by the analysis system, to produce a recycled processing liquid for use in the substrate processing apparatus.

5. the replenisher liquid is an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine and / or an aqueous solution (liquid B) containing an organic solvent and an alkanolamine, 5. The substrate processing system according to claim 4, further comprising a control unit that controls the supply amount of the solution A and / or the solution B that is replenished to the solution C based on the amount of alkanolamine determined by the analysis system.

6. A method for stripping a resin mask, comprising: stripping the resin mask from a substrate having the resin mask thereon, using the substrate processing system according to claim 4.

7. A method for manufacturing an electronic component, comprising the method for removing a resin mask according to claim 6.

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